The influence of casting centrifugation process parameters, such as a rotation speed (ω), the amount of the film-forming solution (V), and its concentration (C) on transport properties of composite membranes were investigated. A number of composite membranes based on poly (1-trimethylsilylpropyne) (PTMSP) and micro- (MFFK-1) and ultrafiltration (UFFK) membranes were obtained using the spin-coating method. For the first time, an unexpected dependence of permeance and ideal selectivity on rotation speed had been discovered: the thickness of the selective layer decreases from 3.0 to 1.0 μm for MFFK-1 and from 1.7 to 1.1 μm for UFFK with an increase of spin coater rotation speed from 500 to 3000 rpm. However, the gas permeance of composite membranes in the range of 500–2000 rpm was reduced due to an increase of a penetration depth of PTMSP into a support layer porous structure (estimated by the EDX method). The permeance of the PTMSP/UFFK membranes was higher than PTMSP/MFFK-1 membranes due to a thinner selective layer and a lower penetration depth of polymer solution into the pores of the support. The highest CO2/N2 selectivity values were achieved as 5.65 ± 0.9 at CO2 permeance 5600 ± 1000 GPU for PTMSP/UFFK membranes (CPTMSP = 0.35%, Vsolution = 1 mL, ω = 1000 rpm), and 6.1 ± 0.5 at CO2 permeance 4090 ± 500 GPU for PTMSP/MFFK-1 membranes (CPTMSP = 0.35%, Vsolution = 1 mL, ω = 2000 rpm).